Surface-treated powder and cosmetic preparation

ABSTRACT

A surface-treated powder powder which is surface-treated with an acrylic/silicone copolymer having at least one hydrolyzable silyl group in the molecule, and a cosmetic material containing this powder. 
     The surface-treated powder of this invention preferably contains 0.1-30 wt parts of the acrylic/silicone copolymer relative to 100 wt parts of the powder prior to surface treatment. The acrylic/silicone copolymer preferably comprises a trunk polymer comprising an acrylic polymer, and a branched polymer comprising an organic polysiloxane. 
     The surface activity of the surface-treated powder of this invention is very well blocked, and it has excellent water resistance and sebum resistance. In addition, the cosmetic material of this invention containing this surface-treated powder has good cosmetic lasting properties, and is highly stable over time.

FIELD OF THE INVENTION

This invention relates to a novel surface-treated powder and cosmeticmaterial containing same, and in particular, to a powder whereof thesurface activity is blocked by surface treatment, and a long-lastingcosmetic material containing this powder which has a smooth feel whenused, dispersibility, water resistance, sebum resistance and stabilitywith time.

BACKGROUND OF THE INVENTION

In general, human secretions such as sweat, tears and sebum spoilcosmetic materials. In particular, with suncut creams and makeupcosmetic materials, sebum secreted by the skin becomes mixed withcosmetic material blending oils, leading to excessive wetting of thecosmetic material which is a major factor causing it to deteriorate. Toreduce the oils in the cosmetic material remaining on the skin, it hasbeen attempted to use volatile oil agents such asoctamethylcyclotetrasiloxane and decamethylcyclopentasiloxane as a partof the oils which were blended.

Rubbing and water are external factors which spoil makeup. To improvepoor makeup lasting properties which occur due to water-solublesubstances, such as sweat and tears, to prevent loss of aqueouscomponents or sebum in the skin and to maintain skin protection,silicone oils are blended to improve water repellence. For example, dueto their light feel, outstanding water-repellence and high safety,silicone oils such as dimethylpolysiloxane have been used abundantly asoils in cosmetic materials in recent years. At the same time, powders,e.g., pigments such as titanium oxide, zinc oxide, red ocher, mica andsericite are widely used in basic cosmetics, suncut materials, nailcolors and nail coats, foundation, mascara and eyeliner. To block thesurface activity of these powders and impart water resistance and sebumresistance, it is common to give them a surface treatment such asalumina treatment, silica treatment, oil treatment, metallic soaptreatment or organopolysiloxane treatment.

In recent years, in many cases, the organopolysiloxane has a reactivepart within the molecule. The organopolysiloxane forms a chemical bondwith the powder, which modifies the powder surface and blocks itssurface activity. Also, the treatment agent does not secede from thepowder surface even if a solvent system cosmetic material is used, andas change of cosmetic material properties due to treatment can bereduced, this is highly effective.

For example, in Japanese Patent (JP-B) No. 2719303, a method of carryingout the surface treatment by 12-60 wt parts of methylhydrogenpolysiloxane to 100 wt parts of powder, is disclosed. In JapaneseUnexamined Patent Publication (JP-A) No. 07-196946, a surface treatmentmethod which uses a straight chain single terminal alkoxy-modifiedsilicone is disclosed. Thus, powder treatment by a reactiveorganopolysiloxane is a generally known technique, however in all cases,the blocking of the powder surface activity was insufficient, and inparticular, when the treatment agent was a methylhydrogenpolysiloxane(methyl hydrogen polysiloxane or dimethylhydrogenpolysiloxane), asunreacted Si—H groups remained in the powder even after surfacetreatment when the powder was blended with the cosmetic material, therewas a problem of hydrogen gas being generated depending on the conditionof liquid properties of the cosmetic material. Moreover, when a powdertreated with a single terminal alkoxy-modified silicone was used as apressed powder cosmetic material, there were few problems regardingwater resistance and sebum resistance, but when it was used in asolution system, the treatment effect could not be said to be adequate.This is considered to be due to few reactive sites which react with thepowder as compared with a methylhydrogen polysiloxane treatment agent,so that untreated parts remain in the powder surface.

Thus, although conventional powders treated by reactiveorganopolysiloxane treatment agents had outstanding aspects, they werenot effective in all forms of cosmetic materials. A surface-treatedpowder with improved blocking of surface activity, water resistance andsebum resistance was therefore desired.

As a result of intensive studies carried out to discover asurface-treated powder with improved blocking of surface activity, waterresistance and sebum resistance, the Inventors found that bysurface-treating the powder with an acrylic/silicone copolymer having atleast one hydrolyzable silyl group in the molecule, a goodsurface-treated powder can be obtained, and by blending thissurface-treated powder with a cosmetic material, a cosmetic materialwhich was very pleasant to use, long-lasting and very stable over timewas obtained, and thereby arrived at the present invention.

It is therefore a first object of the invention to provide asurface-treated powder having an improved surface treatment (blocking ofsurface activity, water resistance and sebum resistance).

It is a second object of the invention to provide a cosmetic materialwhich is very pleasant to use, long-lasting and very stable over time.

SUMMARY OF THE INVENTION

The aforesaid objects of the invention were attained by asurface-treated powder which is surface-treated by an acrylic/siliconecopolymer having at least one hydrolyzable silyl group in the molecule,and by a cosmetic material containing this powder.

The surface-treated powder of the present invention is a powder which issurface-treated by an acrylic/silicone copolymer having at least onehydrolyzable silyl group in the molecule, the proportion of thisacrylic/silicone copolymer preferably being 0.1-30 wt parts relative to100 wt parts of the powder prior to surface treatment.

The aforesaid acrylic/silicone copolymer preferably comprises a trunkpolymer comprising an acrylic polymer, and a branch polymer comprisingan organopolysiloxane.

Further, the acrylic/silicone copolymer is preferably obtained bycopolymerization of 1-97 wt % of the organopolysiloxane compoundrepresented by the following general formula (1),

wherein, A in the formula is the radical polymerizing group representedby:CH₂═C(R²)COOR³  (4)CH₂═C(R²)C₆H₅—  (5)(in the formulae, R² is hydrogen or a methyl group, R³ is an alkylenegroup having 1-10 carbon atoms, and n is 3-500), and R¹ are organicgroups selected from alkyl groups, aryl, aralkyl andfluorine-substituted alkyl groups having 1-30 carbon atoms, which may beidentical or different;0-95 wt % of the acrylic-monomer represented by the following generalformula (2):CH₂═C(R⁴)COOR⁵  (2)wherein, R⁴ in the formula is hydrogen or methyl, and R⁵ is an alkylgroup having 1-30 carbon atoms;and 1-10 wt % of the radical polymerizing silane compound represented bythe following general formula (3):B—Si(CH₃)_(3-m)(OR⁶)_(m)  (3)wherein, B in the formula is a radical polymerizing group having thefollowing general formula (6) or (7):CH₂═C(R⁷)COOR⁸—  (6)CH₂═C(R⁷)C₆H₅—  (7)

wherein, R⁷ is hydrogen or methyl, R⁸ is an alkylene group having 1-10carbon atoms, and R⁶ is an alkyl or alkenyl group having 1-4 carbonatoms, and m is 1-3.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The surface-treated powder of the present invention is obtained bytreating a powder with an acrylic/silicone copolymer having at least onehydrolyzable silyl group in the molecule. There is no particularlimitation on this acrylic/silicone copolymer provided that it has atleast one hydrolyzable silyl group in the molecule. It may be a blockcopolymer or a graft copolymer, but from the viewpoint of adsorption onthe powder, reactivity therewith and properties of the surface-treatedpowder, it is preferably an acrylic/silicone-graft copolymer wherein thetrunk polymer is an acrylic polymer and the branch polymer is anorganopolysiloxane.

There is no particular limitation on the method of manufacturing thisacrylic/silicone graft polymer. The organopolysiloxane may be made toreact with the acrylic-polymer manufactured beforehand, but from theviewpoint of ease of manufacture and molecular design, the macromonomermethod, wherein an organopolysiloxane compound having the radicalpolymerizing group represented by the following general formula (1), theacrylic monomer represented by the following general formula (2), andthe radical polymerizing silane compound represented by the followinggeneral formula (3) are copolymerized together, is convenient.

wherein, A in the formula is a radical polymerizing group represented bythe following general formulae (4) or (5):CH₂═C(R²)COOR³—  (4)CH₂═C(R²)C₆H₅—  (5)(wherein, R² is hydrogen or methyl, R³ is an alkylene group having 1-10carbon atoms and n is 3-500), and R¹ are organic groups selected fromalkyl groups, aryl, aralkyl and fluorine-substituted alkyl groups having1-30 carbon atoms, and may be identical or different.

The organopolysiloxane compound having the radical polymerizing grouprepresented by the aforesaid general formula (1) is known as a siliconemacromonomer, and it has a radical polymerizing group at only oneterminal. Herein, A may be a monovalent organic group having radicalpolymerizing properties, and can be specifically represented by theaforesaid general formulae (4) or (5). Examples of A are (meth)acryloxymethyl, (meth)acryloxy propyl, (meth)acryloxy decyl, styryl andalpha-methylstyryl. Examples of R¹ are alkyl groups such as methyl,ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl andcyclohexyl, aryl groups such as phenyl and tolyl, aralkyl groups such asbenzyl and phenethyl, and fluorine-substituted alkyl groups such astrifluoropropyl and nonafluorobutylethyl, but from the viewpoint ofdispersibility in solvent when the surface-treated powder is blendedwith the cosmetic material, water resistance of the makeup film, sebumresistance and feel, it is preferably mostly methyl.

n is an integer in the range 3-500, but preferably 9-200. If it is lessthan 3, the properties of the silicone are poor, so dispersibility insolvent when the surface-treated powder is blended with the cosmeticmaterial, water resistance of the makeup film and sebum resistance areinadequate, whereas if it is more than 500, copolymerizing propertieswith the acrylic monomer or radical polymerizing silane compound arepoorer, and it is difficult to obtain a good copolymer.

The organopolysiloxane compound having the radical polymerizing groupshown by the aforesaid formula (1) may be synthesized by the methoddescribed in JP-A No. 07-224168, specific examples being as shown below.

wherein, R⁴ is hydrogen or methyl, and R⁵ is an alkyl group having 1-30carbon atoms.

Specific examples of the acrylic monomer of the aforesaid generalformula (2) are methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl(meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate andcyclohexyl (meth)acrylate, 2-ethyl hexyl (meth)acrylate, tridecyl(meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate andbehenyl (meth)acrylate. These may be used alone, or two or more may beused together.B—Si(CH₃)_(3-m)(OR⁶)_(m)  (3)wherein, B is the radical polymerizing group represented by thefollowing general formulae (6) or (7):CH₂═C(R⁷)COOR⁸—  (6)CH₂═C(R⁷)C₆H₅—  (7)(wherein, R⁷ is hydrogen or methyl, R⁸ is an alkylene group having 1-10carbon atoms, R⁶ is an alkyl group or alkenyl group having 1-4 carbonatoms, and m is 1-3).

The hydrolyzable silyl group of the present invention is preferably asilyl group represented by the following formula:—Si(CH₃)_(3-m)(OR⁶)_(m)(wherein, R⁶ and m are identical to the above), and this is introducedinto the acrylic/silicone copolymer of the invention by the radicalpolymerizing silane compound represented by the aforesaid generalformula (3).

B in the radical polymerizing silane compound represented by the generalformula (3), is an identical group to the aforesaid A. Examples of theradical polymerizing silane compound represented by this general formula(3), are:

-   γ-methacryloxypropyl trimethoxysilane, γ-methacryloxypropyl    methyldimethoxysilane, γ-methacryloxypropyl dimethylmethoxysilane,    γ-methacryloxypropyl triethoxysilane, γ-methacryloxypropyl    methyldiethoxysilane, γ-methacryloxypropyl tributoxysilane,    γ-methacryloxypropyl triisopropenoxysilane; γ-acryloxypropyl    trimethoxysilane, acryloxy methyltrimethoxysilane, γ-acryloxypropyl    triethoxysilane, γ-acryloxypropyl methyldiethoxysilane, styryl    trimethoxysilane, styryl triethoxysilane and α-methyl styryl    trimethoxysilane. These may be used alone, or two or more may be    used together.

The proportion of compounds represented by the aforesaid generalformulae (1), (2) and (3) used for copolymerization, is such that theorganopolysiloxane compound having the radical polymerizing group ofgeneral formula (1) is 1-97 wt %, but preferably 5-90 wt %, the acrylicmonomer of general formula (2) is 0-95 wt %, but preferably 2-60 wt %,and the radical polymerizing silane compound of general formula (3) is1-10 wt %, but preferably 2-7 wt %.

When there is too little of the organopolysiloxane compound having theradical polymerizing group of general formula (1), dispersibility inoils when blending the surface-treated powder with the cosmeticmaterial, water resistance of makeup film and sebum resistance are notfully acquired, but if it is too large, adsorption and reactivity withpowder falls. If there is too much of the acrylic monomer of generalformula (2), water resistance of the makeup film and sebum resistanceare not fully acquired. Moreover, if there is too little of the radicalpolymerizing silane compound of general formula (3), reactivity willfall, and if it is too large, reactions occur not only on the powdersurface but also within the treatment agent, so the powder easilycondenses.

Although this acrylic/silicone-graft copolymer can be obtained bycopolymerization of the aforesaid components, it is also possible to useother radical polymerizing compounds within a range which does notimpair the features of the invention, if required. Examples of theseother radical polymerizing compounds are carboxylic acids such as(meth)acrylic acid, fumaric acid and maleic acid, hydroxyalkyl esterssuch as (meth)acrylic acid hydroxyethyl and (meth)acrylic acidhydroxypropyl, amides such as (meth)acrylamide, fluorine-substitutedalkyl esters such as (meth)acrylic acid perfluorooctyl ethyl and(meth)acrylic acid perfluorobutylethyl, styrene, acrylonitrile, vinylacetate, vinyl pyrrolidone, polyoxyethylene mono(meth)acrylate,polyoxypropylene mono(meth)acrylate, polyoxyethylene/polyoxypropylenemono(meth)acrylate, polycaprolactone mono(meth)acrylate,tris(trimethylsiloxy) silylpropyl methacrylate and tris(trimethylsiloxy)silylstyrene.

The molecular weight of the acrylic/silicone copolymer used for thesurface-treated powder of the invention is not particularly limitedprovided that it has at least one hydrolyzable silyl group in themolecule, but it may be 5,000-200,000 expressed as weight averagemolecular weight of polystyrene as measured by GPC. If it is less than5,000, the powder treatment effect is unsatisfactory, and if it is morethan 200,000, it is more difficult to use the surface-treated powderwhen it is blended with the cosmetic material.

The method of manufacturing the acrylic/silicone-copolymer is notparticularly limited and any prior art method may be used such assolution polymerization, emulsion polymerization, suspensionpolymerization and block polymerization, but from the viewpoint ofpolymer homogeneity and ease of molecular weight adjustment, solutionpolymerization is the most preferred. In this case, the solvent used ispreferably one in which the aforesaid components and polymer can beuniformly dissolved. Examples of such solvents are toluene, xylene,ethanol, isopropyl alcohol, n-butanol, acetone, methyl ethyl ketone,methyl isobutyl ketone, ethyl acetate, n-butyl acetate, isobutylacetate, diethyl ether and tetrahydrofuran. As polymerization initiator,the usual radical polymerization initiators may be used, e.g., organicperoxides such as benzoyl peroxide and dicumyl peroxide, and azocompounds such as azobisisobutyronitril. To control the molecular weightof the polymer, mercapto compounds, such as dodecyl mercaptan andmercaptopropyltrimethoxy silane, may be used as a chain transfer agent,and, in the case of a hydrolyzable silyl group-containing compound suchas mercaptopropyltrimethoxy silane, there is also the advantage that thehydrolyzable silyl group is introduced at the polymer end. The obtainedpolymer solution may be used as is or diluted for powder treatment, orthe solvent may be removed and the polymer extracted alone, or it may beredissolved in another solvent and then used.

Provided that it is any of the powders commonly used for cosmeticmaterials, the powder used as the surface-treated powder of theinvention may have any form (spherical, acicular, tabular), particlediameter (fume, fine particle, pigment) or particle structure (porous,non-porous). Examples are inorganic powders, organic powders, surfactantmetal salt powders, colored pigments, pearl pigments, metal powderpigments and natural pigments.

Example of inorganic powders are titanium dioxide, zirconium oxide, zincoxide, cerium oxide, magnesium oxide, barium sulfate, calcium sulfate,magnesium sulfate, calcium carbonate, magnesium carbonate, talc, mica,kaolin, sericite, muscovite, synthetic mica, phlogopite, lepidolite,biotite, lithia mica, silicic acid, silicic anhydride, aluminumsilicate, magnesium silicate, magnesium aluminum silicate, calciumsilicate, barium silicate, strontium silicate, metal tungstates,hydroxyapatite, vermiculite, haidilite, bentonite, montmorillonite,hectorite, zeolite, ceramic powder, dibasic calcium phosphate, alumina,aluminum hydroxide, boron nitride and silica etc.

Examples of organic powders are polyamide powder, polyester powder,polyethylene powder, polypropylene powder, polystyrene powder,polyurethane, benzoguanamine powder, polymethyl benzoguanamine powder,polytetrafluoroethylene powder, polymethylmethacrylate powder,cellulose, silk powder, nylon powder such as nylon 12 and nylon 6,crosslinked silicone fine powder having dimethylsilicone crosslinks,polymethyl silsesquioxane, styrene-acrylic acid copolymer,divinylbenzene-styrene copolymer, vinyl resin, urea resin, phenol resin,fluororesin, silicon resin, acrylate resin, melamine resin, epoxy resin,polycarbonate resin, microcrystalline fiber powder, starch powder andlauroyl lysine.

Examples of surfactant metal salt powders (metallic soaps) are zincstearate, aluminum stearate, calcium stearate, magnesium stearate, zincmyristate, magnesium myristate, zinc cetyl phosphate, calcium cetylphosphate and zinc sodium cetyl phosphate. Examples of colored pigmentsare inorganic red pigments such as iron oxide, iron hydroxide and irontitanate, inorganic brown pigments such as γ-iron oxide, inorganicyellow pigments such as iron oxide yellow and ocher, inorganic blackpigments such as iron oxide black and carbon black, inorganic violetpigments such as manganese violet and cobalt violet, inorganic greenpigments such as chromium hydroxide, chromium oxide, cobalt oxide andcobalt titanate, inorganic blue pigments such as Prussian blue andultramarine blue, lakes of tar pigment, lakes of natural dyes andsynthetic resin powders which are complexes of these powders.

Examples of pearl pigments are titanium dioxide-coated mica, bismuthoxychloride, titanium dioxide-coated bismuth oxychloride, titaniumdioxide-coated talc, scales foil and titanium dioxide-coated coloredmica; examples of metal powder pigments are aluminum powder, copperpowder and stainless steel powder; examples of tar pigments are Red No.3, Red No. 104, Red No. 106, Red No. 201, Red No. 202, Red No. 204, RedNo. 205, Red No. 220, Red No. 226, Red No. 227, Red No. 228, Red No.230, Red No. 401, Red No. 505, Yellow No. 4, Yellow No. 5, Yellow No.202, Yellow No. 203, Yellow No. 204, Yellow No. 401, Blue No. 1, BlueNo. 2, Blue No. 201, Blue No. 404, Green No. 3, Green No. 201, Green No.204, Green No. 205, Orange No. 201, Orange No. 203, Orange No. 204,Orange No. 206 and Orange No. 207; and examples of natural pigments arepowders selected from among carminic acid, laccainic acid, carthamin,bradilin and crocin.

Also in these powders, according to the present invention, extenderssuch as zinc oxide, titanium dioxide or mica, sericite, talc or kaolin,are preferred.

The acrylic/silicone-copolymer used as surface treatment agent for thesepowders may be used for any of its various applications, but it becameclear that it is particularly suitable as a powder surface treatmentagent. The surface-treated powder of the invention which has beensurface-treated with this acrylic/silicone-copolymer has sufficientsurface activity blockage with excellent water resistance and sebumresistance, and does not generate hydrogen after treatment, so it isparticularly useful for cosmetic materials. In this case, the blendingamounts of acrylic/silicone-copolymer and powder are preferably 0.1-30wt parts and more preferably 0.5-10 wt parts to 100 wt parts of powder.

The powder which is surface-treated by the acrylic/silicone-copolymer ofthe invention may be obtained for example by using theacrylic/silicone-copolymer as a treatment agent in a well-knowntreatment method selected from the following treatment methods.

1. The target powder is surface-treated by dispersing it in a treatmentagent comprising water or an organic solvent blended with the treatmentagent.

2. The powder and treatment agent are mixed, and surface treatment iseffected using a crusher such as a ball mill or jet mill.

3. The treatment agent is blended with a solvent, the powder isdispersed therein and the agent is adsorbed on the surface, then theproduct is dried and sintered.

The surface-treated powder of the present invention can be used forvarious kinds of applications, but is particularly useful as a startingmaterial for all cosmetic materials used on the skin and hair, such asskin care products, makeup products, hair products, antiperspirants andultraviolet blocking products. Although it depends on the type and formof the cosmetic material, according to the invention, thesurface-treated powder which has been surface-treated with the aforesaidacrylic/silicone-copolymer can be blended in a proportion of 0.1 to 99%wt parts relative to the whole cosmetic material.

The cosmetic material of the present invention contains the aforesaid A)surface-treated powder as an essential ingredient, and may also furtherat least one moeity selected from among a group comprising B) oils, C)water, D) compounds having an alcoholic hydroxyl group in the molecularstructure, E) water-soluble or water-swelling polymers, F) powdersand/or colorants other than the surface-treated powder of thisinvention, G) surfactants, H) crosslinked organopolysiloxanes, and I)silicone resins.

According to the purpose, one, two or more of the B) oils can be blendedwith the cosmetic material of the invention. If used for an ordinarycosmetic material, any oil may be used. i.e., a solid, semi-solid orliquid oil.

It is moreover preferred that at least part of the oil B) is a liquid atordinary temperature and that at least part of the oil B) is a straightchain or cyclic silicone oil represented by R⁹ _(a)SiO_((4-a)/2)(wherein, R⁹ is an organic group selected from among a hydrogen atom, analkyl group, an aryl group, an aralkyl group and a fluorine-substitutedalkyl group having 1-30 carbon atoms, and 0<=a<=2.5), and particularlypreferred that at least part of the oil B) is an oil comprising afluorine group or an amino group.

Examples of natural animal and vegetable oils and fats, andsemi-synthetic oils and fats, are avocado oil, linseed oil, almond oil,Ibota wax, perilla oil, olive oil, cacao butter, kapok wax, kaya oil,carnauba wax, Glycyrrhiza oil, candellila wax, beef tallow, neat's footoil, beef bone fat, hydrogenated beef tallow, apricot kernel oil,spermaceti wax, hydrogenated oil, wheat germ oil, sesame oil, rice germoil, rice bran oil, sugar cane wax, sasanqua oil, safflower oil, sheabutter, Chinese tung oil, cinnamon oil, jojoba wax, shellac wax, turtleoil, soybean oil, tea seed oil, camellia oil, evening primrose oil, cornoil, lard, rape seed oil, Japanese tung oil, rice-bran oil, germ oil,horse fat, persic oil, palm oil, palm kernel oil, castor oil,hydrogenated castor oil, caster oil fatty acid methylester, sunfloweroil, grapeseed oil, bayberry wax, jojoba oil, macadamia nut oil,beeswax, mink oil, cottonseed oil, cotton wax, Japanese wax, kernel oil,montan wax, coconut oil, hydrogenated coconut oil, tricoconut oil fattyacid glyceride, mutton-tallow, peanut oil, lanolin, liquid lanolin,hydrogenated lanolin, lanolin alcohol, hard lanolin, lanolin acetate,lanolin fatty acid isopropyl, hexyl laurate, POE lanolin alcohol ether,POE lanolin alcohol acetate, polyethylene glycol lanolin fatty acid, POEhydrogenated lanolin alcohol ether, and egg yolk oil. POE meanspolyoxyethylene.

Examples of a hydrocarbon oil which can be mixed therein includeozokerite, squalane, squalene, ceresine, paraffin, paraffin wax, liquidparaffin, pristane, polyisobutylene, microcrystalline wax and Vaseline;and those of a higher fatty acid which can be mixed include lauric acid,myristic acid, palmitic acid, stearic acid, behenic acid, undecylenicacid, oleic acid, linoleic acid, linolenic acid, arachidonic acid,eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), isostearic acidand 12-hydroxystearic acid.

Examples of a higher alcohol which can be mixed therein include laurylalcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, behenylalcohol, hexadecyl alcohol, oleyl alcohol, isostearyl alcohol,hexyldodecanol, octyldodecanol, cetostearyl alcohol,2-decyltetradecinol, cholesterol, phytosterol, POE cholesterol ether,monostearyl glycerin ether (batyl alcohol) and monooleyl glyceryl ether(cerakyl alcohol).

Examples of an ester oil which can be mixed therein include diisobutyladipate, 2-hexyldecyl adipate, di-2-heptylundecyl adipate, N-alkylglycolmonoisostearates, isocetyl isostearate, trimethylolpropane triisostearicacid ester, ethylene glycol di-2-ethylhexanoic acid ester, cetyl2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoic acid ester,pentaerythritol tetra-2-ethylhexanoic acid ester, cetyl octanoate,octyldodecyl gum ester, oleyl oleate, octyldodecyl oleate, decyl oleate,neopentyl glycol dicapric acid ester, triethyl citrate, 2-ethylhexylcinnamate, amyl acetate, ethyl acetate, butyl acetate, isocetylstearate, butyl stearate, diisopropyl sebacate, di-2-ethylhexylsebacate, cetyl lactate, myristyl lactate, isopropyl palmitate,2-ethylhexyl palmitate, 2-hexyldecyl palmitate, 2-heptylundecylpalmitate, cholesteryl 12-hydroxystearate, dipentaerythritol fatty acidesters, isopropyl myristate, octyldodecyl myristate, 2-hexyldecylmyristate, myristyl myristate, hexyldecyl dimethylocanoate, ethyllaurate, hexyl laurate, N-lauroyl-L-glutaminic acid 2-octyldodecyl esterand diisostearyl malic acid; and examples of a glyceride oil which canbe mixed therein include acetoglyceride, triisooctanoic acid glyceride,triisostearic acid glyceride, triisopalmitic acid glyceride,tri-2-ethylhexanoic acid glyceride, monostearic acid glyceride,di-2-heptylundecanoic acid glyceride, trimyristic acid glyceride andmyristic acid isostearic acid diglyceride.

As examples of other silicone oils which can be mixed, mention may bemade of organopolysiloxanes having from low to high viscosities, such asdimethylpolysiloxane, methylphenylpolysiloxane,methylhydrogenpolysiloxane and dimethylsiloxane-methylphenylsiloxanecopolymer; cyclosiloxanes, such as octamethylcyclotetrasiloxane,decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane,tetramethyltetrahydrogencyclotetrasiloxane; silicone rubbers, such asgummy dimethylpolysiloxanes having high polymerization degrees and gummydimethylsiloxane-methylphenylsiloxane copolymers having highpolymerization degrees; and cyclosiloxane solutions of silicone rubber,trimethylsiloxysilicate, cyclosiloxane solutions oftrimethylsiloxysilicate, higher alkoxy-modified silicones such asstearoxysilicone, higher fatty acid-modified silicones, alkyl-modifiedsilicones, amino-modified silicones, fluorine-modified silicones, andsilicone resin solutions. Examples of fluorinated oils are fluoropolyether, perfluorodecalin and perfluorooctane.

The blending amount of these oils B) depends on the oil type, but 1-98wt % of the whole cosmetic material is suitable.

C) water can be blended with the cosmetic material of this inventionaccording to the purpose. The blending amount depends on the type ofagent, but 1-95 wt % of the whole cosmetic material is suitable.

One, two or more of the compounds D) having an alcoholic hydroxyl groupin the molecular structure can be blended with the cosmetic material ofthis invention according to the purpose.

The compound D) having an alcoholic hydroxyl group in its molecularstructure is preferably a water-soluble monohydric alcohol and/or awater-soluble polyhydric alcohol.

Examples of compounds having an alcoholic hydroxyl group which can beadded in this invention are lower alcohols such as ethanol andisopropanol, sugar alcohols such as sorbitol and maltose, sterols suchas cholesterol, sitosterol, phytosterol and lanosterol, and polyhydricalcohols such as butylene glycol, propylene glycol and dibutyleneglycol. The blending amount may be within the range of 0.1-98 wt % ofthe whole cosmetic material.

The cosmetic material of this invention may also contain one, two ormore of E) the water-soluble or water-swelling polymers.

Examples are gum arabic, tragacanth, arabino galactan, (carob gum), guargum, karaya gum, carrageenan, pectin, agar, quince seed (i.e., marmelo)starch (rice, corn, potato, wheat), alge colloid, tranto gum and locustbean gum; microbial polymers, such as xanthan gum, dextran,succinoglucan and pullulan; animal derived polymers, such as collagen,casein, albumin and gelatin; starch derived polymers, such ascarboxymethyl starch and methylhydroxypropyl starch; cellulose polymers,such as methyl cellulose, ethyl cellulose, methylhydroxypropylcellulose, carboxymethyl cellulose, hydroxymethyl cellulose,hydroxypropyl cellulose, nitrocellulose, sodium cellulose sulfate,sodium carboxymethylcellulose, crystalline cellulose and powderycellulose; alginic acid derived polymers, such as sodium alginate andpropylene glycol ester of alginic acid; vinyl polymers, such aspolyvinyl methyl ether and carboxyvinyl polymer; polyoxyethylenepolymers; polyoxyethylene-polyoxypropylene copolymers; acrylic polymers,such as sodium polyacrylate, polyethylacrylate and polyacrylamide; othersynthetic water-soluble polymers, such as polyethyleneimines andcationic polymers; and inorganic water-soluble polymers, such asbentonite, aluminum magnesium silicate, montmorillonite, beidellite,nontronite, saponite, hectorite and silicic acid anhydride. In thesewater-soluble polymers, film-forming agents, such as polyvinyl alcoholand polyvinyl pyrrolidine, are also included. The blending amount iswithin the range of 0.1-25 wt % of total cosmetic material.

One, two or more of the powders and/or colorants F) other than theaforesaid surface-treated powder cosmetic materials A) of this inventionmay be used according to the purpose.

It is preferred that at least part of F), the powder and/or colorant, isa crosslinked silicone fine powder with dimethyl silicone crosslinks,polymethylsilsesquioxane powder, hydrophobic silica or a complex finepowder wherein a spherical silicone rubber surface is coated withpolymethylsilsesquioxane particles, and more preferred that at leastpart of this F) powder and/or colorant is a powder and/or coloranthaving a fluorine group.

As in the case of the powder used as the A) surface-treated powder,provided that it is a powder used for ordinary cosmetic materials, thepowder may have any form (spherical, acicular, tabular), particlediameter (fume, fine particle, pigment) or particle structure (porous,non-porous). Examples are inorganic powders, organic powders, surfactantmetal salt powders, colored pigments, pearl pigments, metal powderpigments and natural pigments.

Complex powders, or powders treated with general oils, silicone oils,fluorine compounds and surfactants, whereof specific examples have beengiven above, may also be used provided that they do not interfere withthe effect of this invention, one, two or more being used as required.The blending amount is preferably 0.1-99 wt % of the total cosmeticmaterial. In particular, the blending amount in the case of a solidpowder cosmetic material is 80-99 wt % of the total cosmetic material.

One, two or more of the G) surfactants can also be used for the cosmeticmaterial of this invention according to the purpose. Examples of suchsurfactants are anionic, cationic, nonionic and amphoteric, there beingno particular limitation, and any surfactant may be used provided thatit is used in ordinary cosmetic materials.

It is preferred that this G) surfactant is a straight chain or branchedsilicone having a polyoxyalkylene chain in the molecule, and it is morepreferred that the HLB of this G) surfactant is 2-8.

Examples of a usable anionic surfactant include fatty acid soap, such assodium stearate or triethanolamine palmitate; alkyl ether carboxylicacids and salts thereof; salts of condensates of amino acids with fattyacids; alkanesulfonates; alkenesulfonates; sulfonated fatty acid esters;sulfonated fatty acid amides; sulfonates of formaldehyde condensatetype; salts of alkylsulfates; salts of higher secondary alcoholsulfates; salts of alkyl and aryl ether sulfates; salts of fatty acidether sulfates, salts of fatty acid alkylolamide sulfates; ethersulfates, such as salts of Turkey red oil sulfate; alkyl phosphatesalts; ether phosphate salts; alkyl allyl ether phosphate salts; amidephosphate salts; and N-acylamino acid type surfactants.

Examples of a usable cationic surfactant include amine salts, such asalkylamine salts, polyamines and aminoalcohol fatty acid derivatives,quaternary alkylammonium salts, quaternary arylammonium salts,pyridinium salts and imidazolium salts.

Examples of a usable nonionic surfactant include sorbitan fatty acidesters, glycerin fatty acid esters, polyglycerin fatty acid esters,propylene glycol fatty acid esters, polyethylene glycol fatty acidesters, sucrose fatty acid esters, polyoxyethylene alkyl ethers,polyoxypropylene alkyl ethers, polyoxyethylene alkyl phenyl ethers,polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acidesters, polyoxyethylene sorbitol fatty acid esters, polyoxyethyleneglycerin fatty acid esters, polyoxyethylene propylene glycol fatty acidesters, polyoxyethylene castor oil, polyoxyethylene hydrogenated castoroil, polyoxyethylene phytostanol ehter, polyoxyethylene phytosterolether, polyoxyethylene cholestanol ether, polyoxyethylene cholesterylether, polyoxyalkylene-modified organopoly-siloxanes,organopolysiloxanes modified with both polyoxyalkylene and alkyl groups,alkanolamides, sugar ethers and sugar amides; and examples of a usableamphoteric surfactant include betaine, aminocarboxylate, imidazolinederivatives and amidoamines. The blending proportion thereof ispreferably in the range of 1-20 wt %, but more preferably 0.2-10 wt %,of the total cosmetic material.

One, two or more types of the H) crosslinked organopolysiloxane can alsobe used in the cosmetic material of this invention. The crosslinkedorganopolysiloxanes suitable for the present cosmetic materials arethose which cause swelling when they contain a silicone having lowviscosity of from 0.65 to 10.0 mm²/sec (25° C.) in an amount larger thantheir own weight. The crosslinking agent of this crosslinkedorganopolysiloxane preferably has two or more vinyl reactive sites inthe molecule, and forms a crosslinked structure by reaction betweenhydrogen atoms directly bonded to silicon atoms. A crosslinkedorganopolysiloxane comprising at least one moeity selected from a groupcomprising polyoxyalkylene, alkyl, alkenyl, aryl and fluoroalkyl in thecrosslinked molecule can also be used. The blending amount when acrosslinked organopolysiloxane is used, is preferably 0.1-50 wt % butmore preferably 1-30 wt %, of the total amount of cosmetic material.

One, two or more of the I) silicone resins can also be used for thecosmetic material of this invention according to the purpose,

This silicone resin is preferably an acrylic silicone resin comprisingan acrylic/silicone graft or block copolymer other than the aforesaidacrylic/silicone-copolymer. An acrylic silicone resin comprising atleast one moeity in the molecule selected from among pyrolidone, longchain alkyl, polyoxy-alkylene, fluoroalkyl portion and anions such ascarboxylic acid, can also be used.

Further, this silicone resin is preferably a silicone reticular compoundrepresented by MQ, MDQ, MT, MDT or MDTQ as a constituent component,wherein M means a mono-functional unit which is able to form a siliconepolymer and is of formula R₃SiO_(1/2), wherein each R is an organicmoiety; D means a di-functional unit which is able to form a siliconepolymer and is of formula R₂SiO, wherein each R is an organic moiety; Tmeans a tri-functional unit which is able to form a silicone polymer andis of formula RSiO_(3/2), wherein R is an organic moiety; and Q means aquad-functional unit which is able to form a silicone polymer and is offormula SiO₂. A silicone reticular compound containing at least onemoeity in the molecule selected from among pyrrolidone, long chainalkyl, polyoxyalkylene, fluoroalkyl and amino can also be used.

The blending amount in the case of using a silicone resin such as anacrylic silicone resin or a silicone reticular compound, is preferably0.1-20 wt %, but more preferably 1-10 wt %, relative to the total amountof cosmetic material.

To the present cosmetic material, the ingredients used in generalcosmetic materials, such as water, a film-forming agent, an oil-solublegelling agent, clay minerals modified with organic compounds, resins,ultraviolet absorbents, a moisture retention agent, antiseptics, anantimicrobial agent, perfume, salts, antioxidants, pH regulators, achelating agent, refreshing agents, an anti-inflammatory agent, skinbeautifying components (a skin whitener, a cell activator, a rough dryskin improver, a blood circulation promoter, a skin astringent and ananti-seborrheic agent), vitamins, amino acids, nucleic acids, hormones,clathrate compounds and hair fixing agents, can be added so far as theyhave no adverse influence on the effects of the present invention.

Examples of an oil-soluble gelling agent which can be added includemetal soaps, such as aluminum stearate, magnesium stearate and zincmyristate; amino acid derivatives, such as N-lauroyl-L-glutamic acid andα,γ-di-n-butylamine; dextrin fatty acid esters, such as dextrin palmiticacid ester, dextrin stearic acid ester and dextrin 2-ethylhexaminic acidpalmitic acid ester; sucrose fatty acid esters, such as sucrose palmiticacid ester and sucrose stearic acid ester; benzylidene derivatives ofsorbitol, such as monobenzylidene sorbitol and dibenzylidene sorbitol;and clay minerals modified with organic compounds, such asdimethylbenzyldodecyl ammonium montmorillonite clay anddimethyldioctadecyl ammonium montmorillonite clay. Examples of anantiperspirant which can be added may be selected from among aluminumchlorohydrate, aluminum chloride, aluminum sesquichlorohydrate, zirconylhydroxychloride, aluminum zirconium hydroxychloride and aluminumzirconium glycine complex.

Examples of an ultraviolet absorbent which can be added includeultraviolet absorbents of benzoic acid type, such as p-aminobenzoicacid; those of anthranilic acid type, such as methyl anthranilate; thoseof salicylic acid type, such as methyl salicylate; those of succinicacid type, such as octyl p-methoxysuccinate; those of benzophenone type,such as 2,4-dihydroxybenzophenone; those of urocanic acid type, such asethyl urocanate; and those of dibenzoylmethane type, such as4-t-butyl-4′-methoxydibenzoylmethane. Examples of an ultravioletabsorption and scattering agent which can be added are powders whichabsorb and scatter ultraviolet light such as fine particle titaniumoxide, fine particle iron-containing titanium oxide, fine particle zincoxide, fine particle cerium oxide and their complexes.

Examples of a moisture retention agent which can be added includeglycerin, sorbitol, propylene glycol, dipropylene glycol, 1,3-butyleneglycol, glucose, xylitol, maltitol, polyethylene glycol, hyaluronicacid, chondroitin sulfuric acid, pyrrolidone carboxylic acid,polyoxyethylene glycoside, and polyoxypropylene methylglycoside.

Examples of an antiseptic agent which can be added include alkylp-oxybenzoates, benzoic acid, sodium benzoate, sorbic acid, potassiumsorbate and phenoxyethanol; and those of an antimicrobial agent whichcan be added include benzoic acid, salicylic acid, carbolic acid, sorbicacid, alkyl p-oxybenzoates, p-chlorometacresol, hexachlorophene,benzalkonium chloride, chlorohexydine chloride, trichlorocarbanilide,photosensitizer and phenoxyethanol.

Examples of an antioxidant which can be added include tocopherol,butylhydroxyanisole, dibutylhydroxytoluene and phytic acid; those of apH regulator which can be added include lactic acid, citric acid,glycolic acid, succinic acid, tartaric acid, dl-malic acid, potassiumcarbonate, sodium hydrogen carbonate and ammonium hydrogen carbonate;those of a chelating agent which can be added include alanine, sodiumethylenediaminetetraacetate, sodium polyphosphate, sodium metaphosphateand phosphoric acid; those of a refrigerant which can be added includeL-menthol and camphor; and those of an anti-inflammatory agent which canadded include allantoin, glycyrrhizin and salts thereof, glycyrrhetinicacid and stearyl glycyrrhetinate, tranexamic acid and azulene.

Examples of a skin-beautifying component which can be added includewhitening agents, such as placenta extract, arbutin, glutathione andYukinoshita extract; cell activators, such as royal jelly,photosensitizer, cholesterol derivatives and calf blood extract; roughdry skin improvers; blood circulation improvers, such as nonylic acidvanillyl amide, benzyl nicotinate, β-butoxyethyl nicotinate, capsaicin,zingerone, cantharis tincture, ichtammol, caffeine, tannic acid,α-borneol, tocopheryl nicotinate, inositol hexanicotinate, cyclandelate,cinnarizine, tolazoline, acetyl choline, verapamil, cepharanthin andγ-oryzanol; skin astringents, such as zinc oxide and tannic acid; andanti-seborrheic agents, such as sulfur and thianthol.

Examples of vitamins which can be added include vitamin A, such asvitamin A oil, retinol, retinyl acetate and retinyl palmitate; vitaminB, including vitamin B2 such as riboflavin, riboflavin butyrate andflavin adenine nucleotide, vitamin B6 such as pyridoxine hydrochloride,pyridoxine dioctanoate and pyridoxine tripalmitate, vitamin B12 and itsderivatives, and vitamin B15 and its derivatives; vitamin C, such asL-ascorbic acid, L-ascorbic acid dipalmitic ester, sodium (L-ascorbicacid)-2-sulfate and dipotassium L-ascorbic acid diphosphate; vitamin D,such as ergocalciferol and cholecarciferol; vitamin E, such asα-tocopherol, β-tocopherol, γ-tocopherol, dl-α-tocopheryl acetate,dl-α-tocopheryl nicotinate and dl-α-tocopheryl succinate; vitamin H;vitamin P; nicotinic acids, such as nicotinic acid, benzyl nicotinateand nicotinic acid amide; pantothenic acids, such as calciumpantothenate, D-pantothenyl alcohol, pantothenyl ethyl ether andacetylpantothenyl ethyl ether; and biotin.

Examples of an amino acid which can be added include glycine, valine,leucine, isoleucine, serine, threonine, phenylaranine, alginine, lysine,aspartic acid, glutamic acid, cystine, cysteine, methionine, andtryptophan; those of a nucleic acid which can be added includedeoxyribonucleic acid; and those of hormone which can be added includeestradiol and ethenyl estradiol.

Examples of a hair fixing polymer compound are amphoteric, anionic,cationic or nonionic polymer compounds, e.g., polyvinylpyrrolidone-polymer compounds such as polyvinyl pyrrolidone and vinylpyrrolidone/vinyl acetate copolymer, acidic vinyl ether polymercompounds such as methyl vinyl ether/maleic anhydride alkyl half estercopolymer, acidic polyvinyl acetate-polymers such as vinylacetate/crotonic acid copolymer, acidic acrylic polymer compounds suchas (meth)acrylic acid/alkyl(meth)acrylate copolymer and (meth)acrylicacid/alkyl(meth)acrylate/alkyl acrylamide copolymer, and amphotericacrylic-polymer compounds such as N-methacryloylethyl-N,N-dimethylammonium-alpha-N-methyl carboxy betaine/alkyl(meth)acrylate copolymer,hydroxypropyl(meth)acrylate/butylaminoethylmethacrylate/ac rylic acidoctylamide copolymer. Also, naturally-occurring polymer compounds suchas cellulose or its derivatives, keratin, and collagen or itsderivatives, can also be used.

The term “cosmetic material” as used herein is intended to include skincare products, such as face lotion, milky lotion, cream, face cleansingcream, packs, oily liquid, massage material, rinsing agent, deodorants,hand cream and lip cream; makeup products such as foundation, powder,liquid foundation, oily foundation, rouge, eye shadow, mascara,eyeliner, eyebrow makeup and lipstick; and hairdressing products, suchas shampoo, rinse, treatment and sets; antiperspirant, and ultravioletdefense cosmetic materials such as suncut milky lotion or suncut cream.

Additionally, the present cosmetic material may have any form, includingliquid, emulsion, cream, solid, paste, gel, powder, compress, layers,mousse, spray, stick or pencil.

EXAMPLES

This invention will now be described in more detail referring tospecific examples, but this invention is not limited thereto. Unlessotherwise specified, “%” refers to “wt %”.

Manufacturing Example 1

100 wt parts of the radical polymerizing organopolysiloxane representedby the following formula (6), 10 wt parts of methyl methacrylate, 80 wtparts of stearyl methacrylate, 10 wt parts ofγ-methacryloxypropyltrimethoxysilane, 200 wt parts of toluene and 4 wtparts of azobisisobutyronitrile were introduced into a glass flaskprovided with a stirrer, thermometer and reflux condenser, and heated ina nitrogen gas stream at 100° C. for 10 hours to carry out apolymerization reaction. Next, the toluene was distilled off underreduced pressure to obtain an acrylic fiber/silicone graft copolymer.This copolymer was a light yellow solid having a melting point of 30° C.The weight average molecular weight expressed as polystyrene by GPC was42,000.

Manufacturing Example 2

In an identical way to that of Manufacturing Example 1, acopolymerization reaction was carried out with 100 wt parts of theradical polymerizing organopolysiloxane represented by formula (6), 60wt parts of methyl methacrylate, 15 wt parts of butyl methacrylate, 15wt parts of 2-ethylhexyl acrylate and 10 parts of γ-methacryloxypropyltriethoxysilane, to obtain an acrylic/silicone graft copolymer.

This copolymer was a light yellow, transparent resin having a meltingpoint of 93° C. The weight average molecular weight expressed aspolystyrene by GPC was 55,000.

Manufacturing Example 3

In an identical way to that of Manufacturing Example 1, acopolymerization reaction was carried out with 180 wt parts of theradical polymerizing organopolysiloxane represented by formula (7), 10wt parts of methyl methacrylate and 10 wt parts of γ-methacryloxypropyltriethoxysilane, to obtain an acrylic/silicone graft copolymer.

This copolymer was a colorless, transparent liquid having a viscosity of270 mm²/sec at 25° C., specific gravity of 0.981 and refractive index of1.4152. The weight average molecular weight expressed as polystyrene byGPC was 11,000.

Examples 1-4 and Comparative Examples 1-4

Surface-treated powders were manufactured according to the followingTable 1 using the acrylic/silicone graft copolymer obtained inManufacturing Examples 1-2, and commercial processing agents.

TABLE 1 Powder Treatment Agent Surface- Tita- Manu- Manu- treated niumfacturing facturing powder oxide Sericite Example 1 Example 2 KF99 KF9901 Example 1 98 2 Example 2 98 2 Example 3 95 5 Example 4 95 5 Comp.Ex. 1 98 2 Comp. Ex. 2 98 2 Comp. Ex. 3 95 5 Comp. Ex. 4 95 5 KF99:Methyl hydrogen polysiloxane, Shin-Etsu Chemical Industries KF9901:Dimethyl methylhydrogen polysiloxane, Shin-Etsu Chemical IndustriesManufacture of Surface-Treated Powder with Above Processing Agents;

98 parts (95 parts sericite) of untreated titanium oxide which hadpreviously been dried under reduced pressure was introduced into areactor, and a solution containing 2 parts (5 parts) of the abovetreatment agent diluted with toluene was gradually added with stirring.The temperature was raised to distil off toluene, and the product bakedat 150° C. for 3 hours to manufacture the surface-treated powders ofExamples 1-4 and Comparative Examples 1-4.

Next, the properties of the surface-treated powder obtained weremeasured regarding surface activity, water resistance and hydrogengeneration amount. The results are shown in Table 2.

TABLE 2 Surface- Surface Water Hydrogen treated activity resistancegeneration powder (δE) (hr) amount (cc/g) Example 1 2.0 6.0 0 Example 21.0 5.5 0 Example 3 2.5 5.5 0 Example 4 1.0 5.0 0 Comp. Ex. 1 2.0 3.52.2 Comp. Ex. 2 4.0 4.5 3.5 Comp. Ex. 3 1.0 6.0 3.5 Comp. Ex. 4 3.0 4.54.0Evaluation Method

Surface activity: 40 parts of the treated powder were kneaded with 60parts of castor oil, a fixed amount was placed between glass slides,irradiated for a fixed time with ultraviolet light, and the colordifference (δE) before and after irradiation was measured.

Water resistance: A fixed amount of the treated powder was pressed by analuminum plate (50 mmΦ), a 1:1 mixture of 1,3-butylene glycol:water wasdripped onto the powder to form water drops, and the absorption time wasmeasured.

Hydrogen generation amount: To measure the remaining amount of Si—Hradicals, a fixed amount of the powder was dispersed in toluene, a 20%KOH alkaline solution was dripped in, the hydrogen was collected, andits volume was measured.

The color change (color difference) increases, the higher is the surfaceactivity of the powder. As can be seen from Table 2, in thesurface-treated powders obtained from the acrylic/silicone graftcopolymer of this invention, in Examples 1-4, no hydrogen at all isgenerated, surface activity is suppressed, and water resistance wasexcellent.

Examples 5-6 and Comparative Examples 5-6

Foundations were prepared having the compositions shown in the followingTable 3 using the surface-treated powder obtained in Examples 1-4 andComparative Examples 1-4, and evaluated.

TABLE 3 Proportion (parts) Ingredient Ex. 5 Ex. 6 Comp.Ex. 5 Comp.Ex. 61 Titanium oxide of 12 — — — Example 1 2 Sericite of Example 3 35 — — —3 Titanium oxide of — 12 — — Example 2 4 Sericite of Example 4 — 35 — —5 Titanium oxide of — — 12 — Comp.Ex. 1 6 Sericite of Comp.Ex. 3 — — 35— 7 Titanium oxide of — — — 12 Comp.Ex. 2 8 Sericite of Comp.Ex. 4 — — —35 9 Lecithin-treated talc 35.1 35.1 35.1 35.1 10 Lecithin-treated 5 5 55 spheroidal nylon powder 11 Red ochre 0.4 0.4 0.4 0.4 12 Yellow ironoxide 2 2 2 2 13 Amber 0.4 0.4 0.4 0.4 14 Black iron oxide 0.1 0.1 0.10.1 15 Dimethylpolysiloxane 7 7 7 7 (6 mm²/sec (25° C.)) 16 Triioctanoicacid glyceryl 1.5 1.5 1.5 1.5 17 Dipentaerithryte fatty 1.5 1.5 1.5 1.5acid ester(Manufacturing Process)

-   A: Ingredients 1-14 were mixed, and uniformly crushed.-   B: Ingredients 15-17 were added to A, and crushed.-   C: B was press-molded to manufacture a powder foundation.

The foundation obtained was tested by an expert panel of 50 women, andease of use, light spreadablity, absence of smears and cosmetic lastingproperties were evaluated according to the following criteria.

Ease of use/cosmetic lasting Lightness of Absence of Rating propertiesspread smearing 5 Good Light Good 4 Fairly good Fairly Fairly good light3 Average Average Average 4 Rather poor Rather Rather poor heavy 1 PoorHeavy Poor

The average points obtained were evaluated judged according to thefollowing criteria.

Average point evaluation:

-   Average point obtained is 4.5 or higher: ⊚-   Average point obtained is 3.5 to 4.5: ◯-   Average point obtained is 2.5 to 3.5: Δ-   Average point obtained is 1.5 to 2.5: x-   Average point obtained is less than 1.5; xx    The results are shown in Table 4.

TABLE 4 Example Example Comp. Comp. 5 6 Ex. 5 Ex. 6 Ease of use ◯ ◯ Δ ◯Lightness of spread ⊚ ⊚ ◯ ◯ Absence of smearing ⊚ ⊚ ◯ ◯ Cosmetic lasting⊚ ⊚ ◯ X properties

As seen from Table 4, the foundations of Examples 5 and 6 not only hadlighter spreadability and were easier to use than those of ComparativeExamples 5 and 6, but they left no smears and had good cosmetic lastingproperties.

Moreover, when Comparative Example 5 which used a powder (ComparativeExamples 1 and 3) treated by KF99 (methylhydrogen polysiloxane) wasstored sealtight in state B of the aforesaid manufacturing methods, thecontainer was observed to swell due to a dehydrogenation reaction ofunreacted Si—H groups.

Method of Manufacturing Various Surface-Treated Powders, and Examples ofVarious Cosmetic Preparations Using these Powders

98 parts of the powders which had been previously heat-treated by dryingunder reduced pressure were introduced into a reactor, and a solutioncomprising 2 parts of one of the aforesaid acrylic/silicone graftcopolymers (Manufacturing Examples 1-3) diluted by toluene was graduallyadded with stirring. The temperature was raised to distil off toluene,and the product was baked at 150° C. for 3 hours with stirring. Thesurface-treated powder obtained was returned to room temperature in acurrent of nitrogen, and used for various cosmetic preparations.

Example 7 Oil-in-Water Type Cream

(Ingredients) Weight (%) 1. Ethanol 17.0 2. Propylene glycol 3.0 3.Polyether-modified silicone (NB 1) 0.5 4. Glyceryl tri-isooctanoate 2.05. Acrylic/ silicone graft copolymer 3.0 (Manufacturing Example 1)-treated sericite 6. Hybrid silicone composite powder (NB 2) 5.0 7.Carboxyvinyl polymer (1% solution) 20.0 8. Xanthan gum (2% solution) 6.09. Triethanolamine 0.2 10. Preservative Suitable amount 11. PerfumeSuitable amount 12. Purified water 60.8 (NB 1) Shin-Etsu ChemicalIndustries Ltd.: KF-6011 (brand name) (NB 2) Shin-Etsu ChemicalIndustries Ltd.: KSP-100 (brand name)(Manufacturing Method)

-   A: Ingredients 1-6 were mixed.-   B: Ingredients 7-12 were mixed and dissolved.-   C: A was added to B, and stirred to form an emulsion.

The oil-in-water cream obtained as described above had a fine texture,spread lightly, was not tacky or oily, was fresh and moist, and left aclean feel. The cosmetic preparation lasted very well, showed no changewith temperature or time, and had excellent stability.

Example 8 Oil-in-Water Type Cream

(Ingredient) Weight (%) 1. Crosslinked dimethylpolysiloxane (NB 1) 10.02. Glyceryl trioctanoate 5.0 3. Dipropylene glycol 7.0 4. Glycerin 5.05. Methylcellulose (2% solution) (NB 2) 7.0 6. Polyacrylamideemulsifying agent (NB 3) 2.0 7. Acrylic/silicone graft copolymer 1.0(Manufacturing Example 2)- treated mica titanium 8. PreservativeSuitable amount 9. Perfume Suitable amount 10. Purified water 63.0(NB 1) Crosslinked dimethylpolysiloxane: KSG-16 (Shin-Etsu ChemicalIndustries Ltd.) (NB 2) Methyl cellulose; Metrose SM-4000 (Shin-EtsuChemical Industries Ltd.) (NB 3): Polyacrylamide emulsifying agent:Sepigel 305 (SEPIC)(Manufacturing Method)

-   A: Ingredients 3-10 were mixed.-   B: Ingredients 1-2 were mixed, dissolved, and added to A with    stirring to form an emulsion.

The oil-in-water type cream obtained as described above had a finetexture, spread lightly, was not tacky or oily, was fresh and moist, andleft a clean feel. The cosmetic preparation lasted very well, showed nochange with temperature or time, and had excellent stability.

Example 9 Water-in-Oil Type Cream

(Ingredient) Weight (%) 1. Dimethylpolysiloxane (6 mm²/sec (25° C.)) 6.02. Methylphenyl polysiloxane 4.0 3. Squalane 5.0 4. Dioctanoic acidneopentyl glycol 3.0 5. Polyether-modified silicone (NB 1) 3.0 6.Hydrophobic particle titanium oxide (NB 2) 2.0 7. Magnesium sulfate 0.78. Glycerin 10.0 9. Preservative Suitable amount 10. Perfurme Suitableamount 11. Purified water Remainder (NB 1) Polyether-modified silicone:KF6012 (Shin-Etsu Chemical Industries Ltd.) (NB 2)Hydrophobically-treated titanium oxide particles: Particulate titaniumoxide having an average particle diameter of 0.05 μm was dispersed inwater to 10 wt %, and sodium silicate solution (SiO₂/Na₂O mole ratio =0.5) was added corresponding to 2 wt % relative to titanium oxide interms of SiO₂, and thoroughly stirred.Next, 10 wt % aluminium sulfatesolution corresponding to 7.5 wt % titanium oxide in terms of Al₂O₃ wasgradually added, and hydrated silicic acid and hydrated alumina weredeposited on the surface of the titanium oxide.After the reaction wascomplete, the product was filtered, washed and dried, and crushed by ajet mill.The product was transferred to a Henschel mixer, 2 wt % of theacrylic/silicone graft copolymer (Manufacturing Example 3) was addedwhile stirring thoroughly, mixed and stirred, and baked at 120° C.(Manufacturing Process)

-   A: Ingredients 1-5 were mixed with heating, ingredient 6 was added,    and the mixture blended uniformly.-   B: Ingredients 7-9 and 11 were dissolved with heating.-   C: B was gradually added to A with stirring to form an emulsion,    cooled, and ingredient 10 was added to obtain a cream.

The water-in-oil type cream obtained as described above had a finetexture, spread lightly, was not tacky or oily, was fresh and moist, andleft a clean feel. The cosmetic preparation lasted very well, showed nochange with temperature or time, and had excellent stability.

Example 10 Water-in-Oil Type Cream

(Ingredient) Weight (%) 1. Alkyl-modified crosslinked 6.0polyether-modified silicone (NB 1) 2. Liquid paraffin 13.5 3. Macadamianut oil 5.0 4. Alkyl/polyether co-modified silicone (NB 2) 0.5 5. Hybridsilicone compound powder (NB 3) 3.0 6. Acrylic/silicone graft copolymer2.0 (Manufacturing Example 2)- treated particulate titanium oxide 7.Sodium citrate 0.2 8. Propylene glycol 8.0 9. Glycerin 3.0 10.Preservative Suitable amount 11. Perfume Suitable amount 12. Purifiedwater 58.8 (NB 1) Alkyl-modified crosslinked polyether-modifiedsilicone: KSG-31 (Shin-Etsu Chemical Industries Ltd.) (NB 2)Alkyl/polyether co-modified silicone: KF-6026 (Shin-Etsu ChemicalIndustries Ltd.) (NB 3) Hybrid silicone composite powder: KSP-100(Shin-Etsu Chemical Industries Ltd.)(Manufacturing Process)

-   A: Ingredients 1-6 were mixed.-   B: Ingredients 7-12 were mixed and dissolved, and A was added with    stirring to form an emulsion.

The cream obtained as described above had a fine texture, spreadlightly, was not tacky or oily, was fresh and moist, and left a cleanfeel. The cosmetic preparation lasted very well, showed no change withtemperature or time, and had excellent stability.

Example 11 Water-in-Oil Type Cream

(Ingredient) Weight (%) 1. Decamethylcyclopentasiloxane 16.0 2.Dimethylpolysiloxane (6 mm²/sec (25° C.)) 4.0 3. Polyether-modifiedsilicone (NB 1) 5.0 4. POE(5) octyldodecyl ether 1.0 5.Mono-polyoxyethylene stearate 0.5 sorbitan (20 E.O.) 6. Anhydroussilicic acid-treated 2.0 zinc oxide (NB 2) 7. Acrylic/silicone graftcopolymer 10.0 (Manufacturing Example 2)- treated particulate titaniumoxide 8. Liquid paraffin 2.0 9. Macadamia nut oil 1.0 10. Scutellariaroot extract (NB 3) 1.0 11. Gentiana extract (NB 4) 0.5 12. Ethanol 5.013. 1,3-butylene glycol 2.0 14. Preservative Suitable amount 15. PerfumeSuitable amount 16. Purified water Remainder (NB 1) Polyether-modifiedsilicone: KF6017 (Shin-Etsu Chemical Industries Ltd.) (NB 2) Anhydroussilicic acid-treated zinc oxide: Silica of particle diameter 0.01–10 μmcontaining 50% occluded zinc oxide; Sansfair SZ-5 (Asahi Glass Ltd.) (NB3) Scutellaria root: exttracted with 50% 1,3 butylene glycol water (NB4) Gentiana extract: extracted with 20% ethanol water(Manufacturing Process)

-   A: Components 6-9 were uniformly mixed and dispersed.-   B: Ingredients 1-5 were mixed, and A was added.-   C: Ingredients 10-14 and 16 were mixed, then B was added to form an    emulsion.-   D: C was cooled, and adding ingredient 15 was added to obtain a    cream.

The water-in-oil type cream thus obtained had a fine texture, was nottacky, spread lightly, had good skin contact, good setting propertiesand sheen. The cosmetic preparation lasted very well, showed no changewith temperature or time, and had excellent stability.

Example 12 Eyeliner

(Ingredient) Weight (%) 1. Decamethylcyclopentasiloxane 39.0 2.Polyether-modified silicone (NB 1) 3.0 3. Organosilicon resin (NB 2)15.0 4. Dioctadecyldimethylammonium salt- 3.0 modified montmorillonite5. Acrylic/silicone graft copolymer 10.0 (Manufacturing Example 1)-treated black iron oxide 6. 1,3-butylene glycol 5.0 7. Sodiumdehydroacetate Suitable amount 8. Preservative Suitable amount 9.Purified water Remainder (NB 1) Polyether-modified silicone: KF-6017(Shin-Etsu Chemical Industries) (NB 2) Organosilicon resin: KF-7312J(Shin-Etsu Chemical Industries)(Manufacturing Process)

-   A: Ingredients 1-4 were mixed, and Ingredient 5 was added.-   B: Ingredients 6-9 were mixed.-   C: B was gradually added to A to form an emulsion, and an eyeliner    was thereby obtained.

The eyeliner obtained as described above spread lightly, was easy todraw with, had a cool, clean feel and was not tacky. It showed no changewith temperature or time, was very easy to use with excellent stability,and not only had superior water and sweat resistance, but also along-lasting effect.

Example 13 Foundation

(Ingredient) Weight (%) 1. Decamethylcyclopentasiloxane 45.0 2. Dimethylpolysiloxane (6 mm²/sec (25° C.)) 5.0 3. Polyether-modified silicone(NB 1) 2.0 4. Octadecyl dimethylbenzyl ammonium 4.0 salt-modifiedmontmorillonite 5. Acrylic/silicone graft copolymer 10.0 (ManufacturingExample 1)- treated titanium oxide 6. Acrylic/silicone graft copolymer6.0 (Manufacturing Example 1)- treated talc 7. Acrylic/silicone graftcopolymer 6.0 (Manufacturing Example 1)- treated mica 8.Acrylic/silicone graft copolymer 1.6 (Manufacturing Example 1)- treatedred ochre 9. Acrylic/silicone graft copolymer 0.7 (Manufacturing Example1)- treated yellow iron oxide 10. Acrylic/silicone graft copolymer 0.2(Manufacturing Example 1)- treated black iron oxide 11. Dipropyleneglycol 5.0 12. Paraoxybenzoic acid methyl ester 0.3 13.2-amino-2-methyl-1,3-propanediol 0.2 14. Hydrochloric acid 0.1 15.Perfume Suitable amount 16. Purified water Remainder (NB 1)Polyether-modified silicone: KF-6017 (Shin-Etsu Chemical Industries)(Manufacturing Process)

-   A: Ingredients 1-5 were mixed with heating, and ingredients 6-11    were added to make a uniform mixture.-   B: Ingredients 12-14 and 16 were dissolved with heating (pH of the    aqueous system is 9.0).-   C: A and B were gradually added with stirring, the mixture was    cooled, and ingredient 15 was added to obtain a foundation.

The foundation obtained as mentioned above had a fine texture, spreadlightly without tackiness or oiliness, was moist and fresh, and left aclean feel. The cosmetic preparation lasted very well, showed no changewith temperature or time, and had excellent stability.

Example 14 Eye Shadow

(Ingredients) Weight (%) 1. Decamethylcyclopentasiloxane 15.0 2.Dimethylpolysiloxane (6 mm²/sec (25° C.)) 10.0 3. Polyether-modifiedbranched 2.0 silicone (NB 1) 4. PEG (10) lauryl ether 0.5 5.Acrylic/silicone graft copolymer 6.2 (Manufacturing Example 2)- treatedchromium oxide 6. Acrylic/silicone graft copolymer 4.0 (ManufacturingExample 2)- treated ultramarine blue 7. Acrylic/silicone graft copolymer6.0 (Manufacturing Example 2)- treated titanium coated mica 8. Sodiumchloride 2.0 9. Propylene glycol 8.0 10. Preservative Suitable amount11. Perfume Suitable amount 12. Purified water Remainder (NB 1)Polyether-modified branched silicone: KF6028 (Shin-Etsu ChemicalIndustries Ltd.)(Manufacturing Process)

-   A: Ingredients 1-4 were mixed, Ingredients 5-7 were added, and    uniformly dispersed.-   B: Ingredients 8-10 and 12 were uniformly dissolved.-   C: B was gradually added to A with stirring to form an emulsion, and    Ingredient 11 was added to obtain an eye shadow.

The eye shadow obtained as mentioned above spread lightly withoutoiliness or powderiness, was moist and fresh, and left a clean feel. Ithad good water resistance, water repellance and sweat resistance. Thecosmetic preparation did not easily disintegrate, showed no change withtemperature or time, and had excellent stability.

Example 15 Lipstick

(Ingredient) Weight (%) 1. Candellila wax 8.0 2. Polyethylene wax 8.0 3.Long-chain alkyl-containing 12.0 acrylic silicone resin (NB 1) 4.Methylphenylpolysiloxane (NB 2) 3.0 5. Isononanic acid isotridecyl 20.06. Isostearic acid glyceryl 16.0 7. Triisostearic acid polyglycyl 28.58. Acrylic/silicone graft copolymer 0.8 (Manufacturing Example 3)-treated red 202 9. Acrylic/silicone graft copolymer 1.5 (ManufacturingExample 3)- treated red ochre 10. Acrylic/silicone graft copolymer 1.0(Manufacturing Example 3)- treated yellow iron oxide 11.Acrylic/silicone graft copolymer 0.2 (Manufacturing Example 3)- treatedblack iron oxide 12. Acrylic/silicone graft copolymer 1.0 (ManufacturingExample 3)- treated titanium oxide 13. Preservative Suitable amount 14.Perfume Suitable amount (NB 1) Long-chain alkyl-containingacrylic/silicone resin: KP-561 (Shin-Etsu Chemical Industries Ltd.) (NB2) Methylphenyl polysiloxane: KF-54 (Shin-Etsu Chemical Industries Ltd.)(Manufacturing Process)

-   A: Ingredients 1-6 and part of 7 were mixed with heated, and    dissolved.-   B: Ingredients 8-14 and the remainder of 7 were uniformly mixed,    added to A and rendered homogeneous.

The lipstick obtained as mentioned above spread lightly without oilinessor powderiness, and left a clean feel. It had good water resistance andwater repellance, lasted well and had excellent stability.

Example 16 Eyeliner

(Ingredient) Weight (%) 1. Decamethylcyclopentasiloxane 6.0 2.Dimethylpolysiloxane (6 mm²/sec (25° C.)) 5.0 3. Jojoba oil 2.0 4.Polyether-modified silicone (NB 1) 1.0 5. Alkyl/polyether co-modifiedsilicone (NB 2) 1.0 6. Acrylic silicone resin (NB 3) 15.0 7.Acrylic/silicone graft copolymer 20.0 (Manufacturing Example 3)- treatedblack iron oxide 8. Ethanol 5.0 9. Preservative Suitable amount 10.Purified water Remainder (NB 1) Polyether-modified silicone: KF6017(Shin-Etsu Chemical Industries Ltd.) (NB 2) Alkyl/polyether co-modifiedsilicone: KF6026 (Shin-Etsu Chemical Industries Ltd.) (NB 3) Acrylicsilicone resin: KP545 (Shin-Etsu Chemical Industries)(Manufacturing Process)

-   A: Ingredients 1-4 were mixed with heating, and Ingredient 5 was    added and uniformly dispersed.-   B: Ingredients 6-8 were dissolved with heating.-   C: B was gradually added to A with stirring to make an emulsion, and    an eyeliner was thus obtained.

The eyeliner obtained as mentioned above spread lightly without oilinessor powderiness, was moist and fresh, and left a clean feel.

It had good water resistance, water repellance and sweat resistance. Thecosmetic preparation did not easily disintegrate, showed no change withtemperature or time, and had excellent stability.

Example 17 Liquid Emulsion Foundation

(Ingredient) Weight (%) 1. Dimethylpolysiloxane (6 mm²/sec (25° C.)) 4.52. Decamethylcyclopentasiloxane 15.0 3. Squalane 4.0 4. Diioctanoic acidneopentyl glycol 3.0 5. Myristic acid isostearic acid diglyceride 2.0 6.α-Monoisostearyl glyceryl ether 1.0 7. Polyether-modified silicons(NB 1) 1.0 8. Alkyl/polyether co-modified silicone (NB 2) 0.5 9.Aluminum distearate 0.2 10. Acrylic/silicone graft copolymer 5.0(Manufacturing Example 2)- treated titanium oxide 11. Acrylic/siliconegraft copolymer 2.0 (Manufacturing Example 2)- treated sericite 12.Acrylic/silicone graft copolymer 3.0 (Manufacturing Example 2)- treatedtalc 13. Acrylic/silicone graft copolymer 0.4 (Manufacturing Example 2)-treated red ochre 14. Acrylic/silicone graft copolymer 0.7(Manufacturing Example 2)- treated yellow iron oxide 15.Acrylic/silicone graft copolymer 0.1 (Manufacturing Example 2)- treatedblack iron oxide 16. Magnesium sulfate 0.7 17. Glycerin 3.0 18.Preservative Suitable amount 19. Perfume Suitable amount 20. Purifiedwater Remainder (NB 1) Polyether-modified silicone: KF6017 (Shin-EtsuChemical Industries Ltd.) (NB 2) Alkyl/polyether co-modified siliicone:KF6026 (Shin-Etsu Chemical Industries Ltd.)(Manufacturing Process)

-   A: Ingredients 1-9 were mixed with heating, and Ingredients 10-15    were added to make a uniform mixture.-   B: Ingredients 16-18 and 20 were dissolved with heating.-   C: B was gradually added to A with stirring, cooled, and Ingredient    19 was added to obtain a liquid emulsification foundation.

The liquid emulsification foundation described above had a lowviscosity, had a fine texture, spread lightly without tackiness oroiliness, was moist and fresh, and left a clean feel. The cosmeticpreparation lasted very well, showed no change with temperature or time,and had excellent stability.

Example 18 Liquid Foundation

(Ingredient) Weight (%) 1. Decamethylcyclopentasiloxane 16.0 2.Dimethylpolysiloxane (6 mm²/sec (25° C.)) 8.0 3. Paramethoxycinnamicacid octyl 3.0 4. 12-hydroxystearic acid 1.0 5. Fluorine-modifiedsilicone (NB 1) 15.0 6. Fluoroalkyl/polyether co-modified 5.0 silicone(NB 2) 7. Spheroidal polymethylsilsesquioxane 3.0 powder (NB 3) 8.Acrylic/silicone graft copolymer 8.0 (Manufacturing Example 1)- treatedparticulate titanium oxide 9. Acrylic/silicone graft copolymer 1.0(Manufacturing Example 1)- treated mica titanium 10. Acrylic/siliconegraft copolymer 5.0 (Manufacturing Example 1)- treated titanium oxide11. Acrylic/silicone graft copolymer 0.9 (Manufacturing Example 1)-treated red ochre 12. Acrylic/silicone graft copolymer 2.0(Manufacturing Example 1) yellow iron oxide 13. Acrylic/silicone graftcopolymer 1.0 (Manufacturing Example 1)- treated black iron oxide 14.Ethanol 15.0 15. Glycerin 3.0 16. Magnesium sulfate 1.0 17. PreservativeSuitable amount 18. Perfume Suitable amount 19. Purified water Remainder(NB 1) Fluorine-modified silicone: FL-50 (Shin-Etsu Chemical IndustriesLtd.) (NB 2) Fluoroalkyl/polyether co-modified silicone: FPD-4694(Shin-Etsu Chemical Industries Ltd.) (NB 3) Spheroidalpolymethylsilsesquioxane powder: KMP590 (Shin-Etsu Chemical IndustriesLtd.)(Manufacturing Process)

-   A: Ingredients 7-13 were uniformly mixed.-   B: Ingredients 1-6 were mixed with heating to 70° C., A was added,    and uniformly mixed and dispersed.-   C: Ingredients 14-17 and 19 were heated to 40° C., B was gradually    added to form an emulsion, cooled, and Ingredient 18 was added to    obtain a liquid foundation.

The liquid foundation obtained as described above was not tacky, spreadliightly, and had a clean, very cool feel. The cosmetic preparationshowed no change with temperature or time, and had excellent stability.

Example 19 Eyeliner

(Ingredient) Weight (%) 1. Decamethylcyclopentasiloxane 22.0 2.Dimethylpolysiloxane (6 mm²/sec (25° C.) 5.0 3. Acrylic/silicone graftcopolymer 20.0 (Manufacturing Example 1)- treated black iron oxide 4.Organosilicon resin (NB 1) 10.0 5. Vitamin E acetate 0.2 6. Jojoba oil2.0 7. Bentonite 3.0 8. Polyether-modified silicone (NB 2) 2.0 9.Ethanol 3.0 10. 1,3-butylene glycol 5.0 11. Preservative Suitable amount12. Purified water Remainder (NB 1) Organosilicon resin: KF-7312J(Shin-Etsu Chemical Industries Ltd.) (NB 2) Polyether-modified silicone:KF6017 (Shin-Etsu Chemical Industries Ltd.)(Manufacturing Process)

-   A: Ingredients 1-2 and 4-7 were mixed, Ingredient 3 was added, and    uniformly mixed and dispersed.-   B: Ingredients 8-10 and 12 were mixed.-   C: B was gradually added to A to make an emulsion, cooled, and    Ingredient 11 was added to obtain an eyeliner.

The eyeliner obtained as mentioned above spread lightly, was easy todraw with, and had a cool, clean feel without tackiness. It showed nochange with temperature or time, was easy to use, and had excellentstability.

It also had excellent water resistance and sweat resistance, and wasfound to last very well.

Example 20 Foundation

(Ingredient) Weight (%) 1. Decamethylcyclopentasiloxane 27.0 2.Methylphenyl polysiloxane 3.0 3. Trioctanic acid glyceryl 10.0 4.Polyether-modified silicone (NB 1) 1.0 5. Mono-isostearic acidpolyglyceryl 3.0 6. Hydrophobically-treated mixed powder (NB 2) 18.0 7.Red ochre 1.2 8. Yellow iron oxide 2.6 9. Black iron oxide 0.2 10.1,3-butylene glycol 7.0 11. Sodium chloride 0.5 12. PreservativeSuitable amount 13. Perfume Suitable amount 14. Ppurified waterRemainder (NB 1) Polyether-modified silicone: KF6017 (Shin-Etsu ChemicalIndustries Ltd.) (NB 2) Hydrophobically-treated mixed powder a. Fineparticulate titanium oxide 8.0 b. Fine particulate zinc oxide 4.0 c.Talc 3.0 d. Mica 3.0(Manufacturing Process)

-   A: Ingredients a-d were mixed, 1 wt % of acrylic/silicone graft    copolymer (Manufacturing Example 1) was added to these powders, and    heat treatment was applied.-   B: Ingredients 1-5 were mixed, dissolved with heating, and    Ingredients 6-9 were uniformly dispersed.-   C: Ingredients 10-12 and 14 were mixed, and B was added to make an    emulsion.-   D: C was cooled, and Ingredient 13 was added to obtain a foundation.

The foundation obtained as described above was not tacky, spreadlightly, had good skin contact, good setting properties and sheen.

The cosmetic preparation lasted very well, showed no change withtemperature or time, and had excellent stability.

Example 21 Brushing Agent Spray

(Ingredient) Weight (%) 1. Myristic acid isopropyl 1.0 2. Stearyltrimethylammonium chloride 0.05 3. Acrylic/silicone graft copolymer 3.0(Manufacturing Example 1)- treated particulate zinc oxide 4. Ethanol25.0 5. Perfume Suitable amount 6. Propellant Remainder(Manufacturing Process)

-   A: Ingredients 1-5 were mixed.-   B: An aerosol can was filled with A, and Ingredient 6 added to    obtain a brushing agent.

The brushing agent spray obtained as described above had a good sheen,was very smooth and had excellent durability. The dispersibility of thepowder was excellent, combing was easy, and a very good result withsheen was obtained.

Example 22 Rinse

(Ingredient) Weight (%) 1. Distearic acid ethylene glycol 3.0 2. Cetanol2.0 3. Mono-stearic acid propylene glycol 3.0 4. Dimethylpolysiloxane(100 mm²/sec (25° C.)) 3.0 5. Mono-stearic acid glycerin 4.0 6.Polyoxyethylene (3) stearate 4.0 7. Acetyl chloride trimethylammonium5.0 8. Polyoxyethylene (20) cetyl ether 2.0 9. Acrylic/silicone graftcopolymer 2.0 (Manufacturing Example 1)- treated zinc oxide 10.1,3-butylene glycol 5.0 11. Preservative Suitable amount 12. PerfumeSuitable amount 13. Purified water Remainder(Manufacturing Process)

-   A: Ingredients 1-9 were stirred, and mixed.-   B: Ingredients 10-11 and 13 were mixed with heating.-   C: B was added to A and mixed, cooled, and Ingredient 12 was added    to obtain a rinse.

The rinse obtained as described above was neither tacky nor heavy inuse, gave an excellent sheen to the hair, and left the hair soft, smoothand full. The preparation was very easy to use while combing the hair,and was highly durable.

Example 23 Rinse-in Shampoo

(Ingredients) Weight (%) 1. Lauric acid amidopropyldimethylaminoacetic15.0 acid betaine (30%) 2. Polyoxyethylene (3) lauryl ether 4.0 sodiumsulfate (27%) 3. Polyoxyethylene (150) distearate 0.5 4. Cationiccellulose (4%) 0.5 5. Glycerin 3.0 6. Dimethyl polysiloxane (1,000,000mm²/sec 1.0 (25° C.)) 7. Dimethyl polysiloxane (100 mm²/sec (25° C.))3.0 8. Acrylic/silicone graft copolymer 2.0 (Manufacturing Example 1)-treated mica 9. Preservative Suitable amount 10. Perfume Suitable amount11. Purified water Remainder(Manufacturing Process)

-   A: Ingredients 1-5, 9 and 11 were heated and mixed.-   B: Ingredients 6-8 were mixed, and dispersed.-   C: B was added to and mixed with A, cooled, and Ingredient 10 was    added to obtain a rinse-in shampoo. The rinse-in shampoo obtained as    described above was neither tacky nor heavy in use, gave an    excellent sheen to the hair, and left the hair soft, smooth and    full. The preparation was very easy to use while combing the hair,    and was highly durable.

Example 24 Treatment

(Ingredient) Weight (%)  1. Distearic acid ethylene glycol 1.0  2.Liquid paraffin 10.0   3. Squalane 5.0  4. Stearyl alcohol 1.5  5.Dimethyl polysiloxane (10 mm²/sec (25° C.)) 3.0  6. Stearic acid 6.0  7.Polyoxyethylene (3) stearyl .alcohol 4.5  8. Polyoxyethylene (150) cetylether 2.0  9. Acrylic/silicone graft copolymer (Manufacturing 1.5   Example 3) - treated sericite 10. 1,3-butylene glycol 6.0 11.Preservative Suitable amount 12. Perfume Suitable amount 13. Purifiedwater Remainder(Manufacturing Process)

-   A: Ingredients 1-9 were heated, and mixed.-   B: Ingredients 10-11 and 13 were mixed, and dispersed.-   C: B was added to and mixed with A, cooled, and Ingredient 12 was    added to obtain a treatment.

The treatment obtained as described above was neither tacky nor heavy inuse, gave an excellent sheen to the hair, and left the hair soft, smoothand full. The preparation was very easy to use while combing the hair,and was highly durable.

Example 25 Water-in-Oil Type Antiperspirant

(Ingredient) Weight (%)  1. Crosslinked polyether-modified silicone(NB 1) 7.0  2. Decamethylcyclopentasiloxane 10.0  3. Trioctanic acidglyceryl 7.0  4. Dipropylene glycol 5.0  5. Sodium citrate 0.2  6.Aluminum/zirconium tetrachlorohydrate 18.0  7. Acrylic/silicone graftcopolymer (Manufacturing 5.0    Example 2) - treated zinc oxide  8.Fluorine-modified hybrid silicone composite 2.0    powder (NB 2)  9.Perfume Suitable amount 10. Purified water 45.8 (NB 1) Crosslinkedpolyether-modified silicone: KSG-21 (Shin-Etsu Chemical Industries Ltd.)(NB 2) Fluorine-modified hybrid silicone composite powder: KSP-200(Shin-Etsu Chemical Industries Ltd.)(Manufacturing Process)

-   A: Ingredients 1-3 were mixed.-   B: Ingredients 4-10 were mixed.-   C: B was added to A, mixed and emulsified.

The water-in-oil antiperspirant obtained as described above spreadlightly, had a cool, clean feel and was not tacky or oily. It showed nochange with temperature or time, was very easy to use and very stable.

Example 26 Roll-On Antiperspirant

(Ingredient) Weight (%)  1. Crosslinked polyether-modified silicone(NB 1) 20.0  2. Dimethylpolysiloxane (6 mm²/sec (25° C.)) 10.0  3.Crosslinked dimethylpolysiloxane (NB 2) 15.0  4. Decamethylcyclopentasiloxane 30.0  5. Aluminum/zirconium tetrachlorohydrate 20.0 6. Acrylic/silicone graft copolymer (Manufacturing  5.0    Example 1) -treated zinc oxide  7. Perfume Suitable amount (NB 1) Crosslinkedpolyether-modified silicone: KSG-21 (Shin-Etsu Chemical Industries Ltd.)(NB 2) Crosslinked dimethyl polysiloxane: KSG-15 (Shin-Etsu ChemicalIndustries Ltd.)(Manufacturing Process)

-   A: Ingredients 1-4 were mixed.-   B: Ingredients 5-7 were added to A, and uniformly dispersed.

The roll-on antiperspirant obtained as described above spread lightly,had a cool, clean feel and was not tacky or oily. It showed no changewith temperature or time, was very easy to use and very stable.

Example 27 Sunscreen Milky Lotion

(Ingredients) Weight (%)  1. Decamethylcyclopentasiloxane 20.0   2.Methylphenylpolysiloxane 3.0  3. Mono-isostearic acid sorbitan 1.0  4.Polyether-modified silicone (NB 1) 0.5  5. Trimethylsiloxysilicic acid(NB 2) 1.0  6. Paramethoxycinnamic acid octyl 4.0  7. Acrylic/siliconegraft copolymer (Manufacturing 8.0    Example 1) - treated particulatetitanium oxide  8. Sorbitol 2.0  9. Sodium chloride 2.0 10. PreservativeSuitable amount 11. Perfume Suitable amount 12. Purified water Remainder(NB 1) Polyether-modified silicone: KF6015 (Shin-Etsu ChemicalIndustries Ltd.) (NB 2) Trimethylsiloxysilicic acid: X-21-5250(Shin-Etsu Chemical Industries Ltd.)(Manufacturing Process)

-   A: Ingredients 1-6 were mixed with heating, and Ingredient 7 was    uniformly dispersed.-   B: Ingredients 8-10 and 12 were mixed with heating.-   C: B was added to A with stirring to form an emulsion, cooled, and    Ingredient 11 was added to obtain a sunscreen milky lotion.

The sunscreen milky lotion obtained as described above had a finetexture, spread lightly, was not tacky, and was fresh and moist. Also,as the cosmetic preparation lasted well, its ultraviolet radiationblocking effect was maintained, it showed no change with temperature ortime, and had excellent stability.

Example 28 Suncut Cream

(Ingredient) Weight (%)  1. Decamethylcyclopentasiloxane 17.5  2.Acrylic silicone resin (NB 1) 12.0  3. Tri isooctanoic acid glyceryl 5.0 4. Paramethoxycinnamic acid octyl 6.0  5. Crosslinkedpolyether-modified silicone (NB 2) 5.0  6. Alkyl/polyether co-modifiedsilicone (NB 3) 1.0  7. Acrylic/silicone graft copolymer (Manufacturing20.0    Example 2) - treated zinc oxide  8. Sodium chloride 0.5  9.1,3-butylene glycol 2.0 10. Preservative Suitable amount 11. PerfumeSuitable amount 12. Purified water Remainder (NB 1) Acrylic siliconeresin: KP545 (Shin-Etsu Chemical Industries Ltd.) (NB 2) Crosslinkedpolyether-modified silicone: KSG21 (Shin-Etsu Chemical Industries Ltd.)(NB 3) Alkyl/polyether co-modified silicone: KF6026 (Shin-Etsu ChemicalIndustries Ltd.)(Manufacturing Process)

-   A: Ingredient 2 was added to part of Ingredient 1 and mixed    uniformly, Ingredient 7 was added, and dispersed by a bead mill.-   B: The remainder of Ingredient 1 and Ingredients 3-6 were mixed, and    blended uniformly.-   C: Ingredients 8-10 and 12 were mixed, and dissolved.-   D: C was added to B to make an emulsion, then A and Ingredient 11    were added to obtain a suncut cream.

The suncut cream obtained as described above was not tacky, spreadlightly, had good skin contact, good setting properties and left theskin silky. The cosmetic preparation lasted very well, showed no changewith temperature or time, and had excellent stability.

INDUSTRIAL USE

The surface-treated powder of this invention treated with theacrylic/silicone graft copolymer compound has blocked surface activity,and excellent water resistance. Therefore, cosmetic preparations whichuse the surface-treated powder of this invention spread lightly, are notoily, are fresh and moist and leave a clean feel. They also have verygood dispersibility, sebum resistance and cosmetic lasting properties.Moreover, they show no change with temperature or time, and haveexcellent stability, which demonstrates the significance of thisinvention.

1. A surface-treated powder which is obtained by treating a surface ofsaid powder with an acrylic/silicone copolymer having at least onehydrolyzable silyl group in its molecule so that said copolymer isadsorbed on the surface of the powder, then dried and sintered, whereinthe powder is at least one selected from the group consisting ofinorganic powders, organic powders, surfactant metal salt powders,colored pigments, pearl pigments, metal powder pigments and naturalpigments; and the proportion of the acrylic/silicone copolymer relativeto 100 wt parts of the powder before surface treatment is 0.1-30 wtparts; wherein the acrylic/silicone copolymer is obtained bycopolymerization of 1-97 wt % of an organopolysilixane compound offormula (1):

wherein, A is a radical polymerizing group of formula (4) or (5):CH₂═C(R²)COOR³—  (4)CH₂═C(R²)C₆H₅—  (5) wherein R² is hydrogen or methyl, R³ is an alkylenegroup having 1-10 carbon atoms, and n is 3-500, R¹ are organic groupsselected from alkyl groups, aryl, aralkyl and fluorine-substituted alkylgroups having 1-30 carbon atoms, which are identical or different; and2-95 wt % of the acrylic monomer of formula (2):CH₂═C(R⁴)COOR⁵  (2) wherein, R⁴ is hydrogen or methyl, and R⁵ is analkyl group having 1-30 carbon atoms; and 1-10 wt % of the radicalpolymerizing silane compound of formula (3):B—Si(CH₃)_(3-m)(OR⁶)_(m)  (3) wherein, B is a radical polymerizing offormula (6) or (7):CH₂═C(R⁷)COOR⁸—  (6)CH₂═C(R⁷)C₆H₅—  (7) wherein, R⁷ is hydrogen or methyl, R⁸ is an alkylenegroup having 1-10 carbon atoms, R⁶ is an alkyl group or alkenyl grouphaving 1-4 carbon atoms, and m is 1-3.
 2. The surface-treated powderaccording to any of claim 1, wherein said powder is zinc oxide, titaniumoxide or an extender pigment.
 3. A cosmetic material comprising the A)surface-treated powder described in any of claim
 1. 4. The cosmeticmaterial according to claim 3, further comprising at least one of B) anoil, C) water, D) a compound having an alcoholic hydroxyl group in itsmolecular structure, E) a water-soluble or water-swelling polymer, F) apowder and/or colorant which is not the surface-treated powder A), G) asurfactant, H) a crosslinked organopolysiloxane, and I) a siliconeresin.
 5. The cosmetic material according to claim 4, wherein at leastpart of said B) oil is a liquid at ordinary temperature.
 6. The cosmeticmaterial according to claim 4, wherein at least part of said B) oil is astraight chain or cyclic silicone oil represented by R⁹_(a)SiO_((4-a)/2) wherein R⁹ is hydrogen or an organic group, which isan alkyl group, aryl group, aralkyl group or fluorine-substituted alkylgroup having 1-30 carbon atoms, and 0<=a<=2.5.
 7. The cosmetic materialaccording to any of claim 4, wherein at least part of said B) oil is anoil having a fluorine group or an amino group.
 8. The cosmetic materialaccording to claim 4, wherein D) the compound having an alcoholichydroxyl group in its molecular structure is a water-soluble, monohydricalcohol and/or a water-soluble polyhydric alcohol.
 9. The cosmeticmaterial according to claim 4, wherein at least part of F) the powderand/or colorant is a crosslinked silicone fine powder having acrosslinked dimethylsilicone structure, a hydrophobic silica, or acomposite powder wherein a spheroidal silicone rubber surface is coatedwith polymethyl silsesquioxane particles.
 10. The cosmetic materialaccording to claim 4, wherein at least part of F) the powder and/orcolorant is a powder and/or colorant comprising fluorine groups.
 11. Thecosmetic material according to claim 4, wherein G) the surfactant is astraight chain or branched silicone having a polyoxyalkylene chain inthe molecule.
 12. The cosmetic material according to claim 4, whereinthe HLB of G) the surfactant is 2-8.
 13. The cosmetic material accordingto claim 4, wherein H) the crosslinked organopolysiloxane is acrosslinked organopolysiloxane containing at least its own weight of asilicone having a low viscosity of 0.65 mm²/sec (25° C.)-10.0 mm²/sec(25° C.).
 14. The cosmetic material according to claim 4, wherein H) thecrosslinked organopolysiloxane is a crosslinked organopolysiloxanecomprising two or more vinylic and reactive sites in the molecule, andis formed by reaction with a hydrogen atom directly bonded to a siliconatom.
 15. The cosmetic material according to any of claim 14, wherein H)the crosslinked organopolysiloxane is a crosslinked organopolysiloxanecomprising at least one part polyoxyalkylene, alkyl, aryl andfluoroalkyl moiety in its crosslinked molecule.
 16. The cosmeticmaterial according to claim 4, wherein I) the silicone resin is anacrylic/silicone resin other than the acrylic/silicone copolymer. 17.The cosmetic material according to claim 4, wherein I) the siliconeresin is an acrylic/silicone resin comprising at least one pyrrolidone,long chain alkyl, polyoxyalkylene, fluoroalkyl or carboxylic acidmoiety.
 18. The cosmetic material according to claim 4, wherein I) thesilicone resin is a reticular silicone compound comprising at least onepyrrolidone, long chain alkyl, polyoxyalkylene, fluoroalkyl or aminomoiety.
 19. The cosmetic material according to any of claim 3, whereinthe form of the product is a liquid, emulsion, cream, solid, paste, gel,powder, compress, laminate, mousse, spray, stick or pencil.
 20. A skincare cosmetic material, comprising a skin care cosmetic material carrierand the cosmetic material according to claim
 3. 21. A makeup cosmeticmaterial, comprising a makeup cosmetic material carrier and the cosmeticmaterial according to claim
 3. 22. A hair care cosmetic material,comprising a hair care cosmetic material carrier and the cosmeticmaterial according to claim
 3. 23. An antiperspirant cosmetic material,comprising an antiperspirant cosmetic material carrier and the cosmeticmaterial according to claim
 3. 24. An ultraviolet defense cosmeticmaterial, comprising an ultraviolet defense cosmetic material carrierand the cosmetic material according to claim
 3. 25. The skin carecosmetic material according to claim 20, wherein the form of the productis a liquid, emulsion, cream, solid, paste, gel, powder, compress,laminate, mousse, spray, stick or pencil.
 26. The makeup cosmeticmaterial according to claim 21, wherein the form of the product is aliquid, emulsion, cream, solid, paste, gel, powder, compress, laminate,mousse, spray, stick or pencil.
 27. The hair care cosmetic materialaccording to claim 22, wherein the form of the product is a liquid,emulsion, cream, solid, paste, gel, powder, compress, laminate, mousse,spray, stick or pencil.
 28. The antiperspirant cosmetic materialaccording to claim 23, wherein the form of the product is a liquid,emulsion, cream, solid, paste, gel, powder, compress, laminate, mousse,spray, stick or pencil.
 29. The ultraviolet defense cosmetic materialaccording to claim 24, wherein the form of the product is a liquid,emulsion, cream, solid, paste, gel, powder, compress, laminate, mousse,spray, stick or pencil.
 30. The surface-treated powder according toclaim 1, wherein the acrylic/silicone copolymer is obtained bycopolymerization of 5-90 wt % of an organopolysiloxane compound offormula (1), 2-60 wt % of an acrylic monomer of formula (2), and 2-7 wt% of a radical polymerizing silane compound of formula (3).
 31. Thesurface-treated powder according to claim 1, wherein the molecularweight of the acrylic/silicone copolymer is 5,000-200,000 expressed asweight average molecular weight of polystyrene as measured by GPC. 32.The surface-treated powder for the cosmetic material according to claim1, wherein 2-60 wt % of an acrylic monomer of formula (2) is used in thecopolymerization.
 33. The surface-treated powder for the cosmeticmaterial according to claim 1, wherein the adsorption is performed bydispersing said powder in a treatment agent comprising theacrylic/silicone copolymer and water or organic solvent; or mixing thepowder with the treatment agent and treating with ball mill or jet mill;then drying and sintering the product.
 34. The surface-treated powderfor the cosmetic material according to claim 1, wherein the adsorptionis performed by dispersing said powder in a treatment agent comprisingthe acrylic/silicone copolymer and water or organic solvent; then dryingand sintering the product.
 35. The surface-treated powder for thecosmetic material according to claim 32, wherein the adsorption isperformed by dispersing said powder in a treatment agent comprising theacrylic/silicone copolymer and water or organic solvent; or mixing thepowder with the treatment agent and treating with ball mill or jet mill;then drying and sintering the product.
 36. The surface-treated powderfor the cosmetic material according to claim 32, wherein the adsorptionis performed by dispersing said powder in a treatment agent comprisingthe acrylic/silicone copolymer and water or organic solvent; then dryingand sintering the product.